Pengchu Zhang

Boehmite Sorbs Perrhenate and Pertechnetate

Boehmite and Al-oxyhydroxide gels sorb ReO4-, a non-radioactive analogue of TcO4- from NaNO3 solutions. Sorption appears to be substantially electrostatic (though there appears to be a specific preference for ReO4- over NO3-) and is most effective at pH < 8. Measured Kd´s lie between 5 and 105 ml g-1, depending on the solid, pH, and ionic strength. ReO4- and TcO4- are both partially removed from high pH Hanford-type acid waste simulants upon neutralization and formation of Al-rich sludges. We therefore propose that sequestration of Tc by boehmite limits dissolved Tc levels in the near and sub-surface environment and for that purpose boehmite might be relied on as a backfill, or reactive barrier, to limit environmental transport of Tc.

Chemical evolution of leaked high-level liquid wastes in Hanford soils

A number of Hanford tanks have leaked high level radioactive wastes (HLW) into the surrounding unconsolidated sediments. The disequilibrium between atmospheric C0{sub 2} or silica-rich soils and the highly caustic (pH > 13) fluids is a driving force for numerous reactions. Hazardous dissolved components such as {sup 133}Cs, {sup 79}Se, {sup 99}Tc may be adsorbed or sequestered by alteration phases, or released in the vadose zone for further transport by surface water. Additionally, it is likely that precipitation and alteration reactions will change the soil permeability and consequently the fluid flow path in the sediments. In order to ascertain the location and mobility/immobility of the radionuclides from leaked solutions within the vadose zone, the authors are currently studying the chemical reactions between: (1) tank simulant solutions and Hanford soil fill minerals; and (2) tank simulant solutions and C0{sub 2}. The authors are investigating soil-solution reactions at: (1) elevated temperatures (60--200 C) to simulate reactions which occur immediately adjacent a radiogenically heated tank; and (2) ambient temperature (25 C) to simulate reactions which take place further from the tanks. The authors studies show that reactions at elevated temperature result in dissolution of silicate minerals and precipitation of zeolitic phases. At 25 C, silicate dissolution is not significant except where smectite clays are involved. However, at this temperature CO{sub 2} uptake by the solution results in precipitation of Al(OH){sub 3} (bayerite). In these studies, radionuclide analogues (Cs, Se and Re--for Tc) were partially removed from the test solutions both during high-temperature fluid-soil interactions and during room temperature bayerite precipitation. Altered soils would permanently retain a fraction of the Cs but essentially all of the Se and Re would be released once the plume was past and normal groundwater came in contact with the contaminated soil. Bayerite, however, will retain significant amounts of all three radionuclides.